N-(cyanoalky)-3,5-dichlorobenzamide

ABSTRACT

New and valuable substituted benzamides having good herbicidal properties and a process for controlling the growth of unwanted plants with these compounds.

United States Patent [191 Rohr et al.

[ 1 Apr. 29, 1975 Adolf Fischer, Mutterstadt, all of Germany [73] Assignee: Badische Anilin- & Soda-Fabrik Aktiengesellschaft, Ludwigshafen (Rhine), Germany 22 Filed: July 17,1972

21 Appl. No.: 272,367

[30] Foreign Application Priority Data Aug. 12, 1971 Germany 2140438 [52] U.S. Cl 260/465 D; 71/105; 71/111; 71/118; 260/471 A; 260/558 D [51] Int. Cl. C07c 103/22; C07c 121/78 [58] Field of Search 260/465 D [56] References Cited UNITED STATES PATENTS 3,457,294 7/1969 Crovetti et a1 260/465 Primary ExaminerLewis Gotts Assistant ExaminerDolph H. Torrence Attorney, Agent, or Firm.lohnston, Keil, Thompson & Shurtleft 5 7] ABSTRACT New and valuable substituted benzamides having good herbicidal properties and a process for controlling the growth of unwanted plants with these compounds.

4 Claims, No Drawings N-(CYANOALKY)-3,5-DICHLOROBENZAMIDE This invention relates to new and valuable substituted benzamides having herbicidal properties, herbicides containing these compounds and the use of these compounds as herbicides.

It is known to use N-(1,1-dimethy1-2-butyny1)-3,5- dichlorobenzamide-as a herbicide. However, its action is unsatisfactory.

We have now found that benzamides of the formula DC-NH-R 01 where R denotes alkyl or alkenyl branched on the carhon atom in a-position to nitrogen and which is unsubstituted or substituted one or more times by halogen, cyano, hydroxy, ether, carbalkoxy, aryl (phenyl) or cycloalkyl (cyclohexyl), or R denotes a,a,B-trimethy1butynyl, a,a-diethylpropyny1, a-methyl-a-ethylpropynyl, a-methylpropynyl, a-methyl-a-ethynylbenzyl or a-methyl-a-ethynylisobutyl, or R denotes a cycloaliphatic radical of a maximum of 1 1 carbon atoms, have a strong herbicidal action.

The compounds have a particularly good action on grassy weeds in the following crops: Soja hispida, Brassica spp., and Lattica spp. at application rates of 1 to 5 kg per hectare.

The compounds are generally prepared by reacting 3,5-dichlorobenzoyl chloride in the presence of an acid acceptor with a suitable amine of the formula where R has the above meanings.

It is preferred to add 3,5-dich1orobenzoyl chloride to a solution of the amine and acid acceptor in a suitable inert solvent. The following may be used as acid acceptors: triethylamine, pyridine, N,N-dimethy1ani1ine, potassium carbonate, sodium carbonate, or an equivalent or excess amount of the amine to be reacted. The solvent may be any inert organic solvent, i. e., a solvent which, under the reaction conditions, does not react with any of the components or with the desired end product. Examples of such solvents are benzene, tetrahydrofuran, toluene, ether, 1,2-diethoxyethane, etc.

The mixture is stirred at a temperature of from to 100C until the reaction is over. The reaction may also be carried out in an aqueous solvent system or in a twophase system comprising one of the water-insoluble s01- vents mentioned above and an acid acceptor such as, for instance, an alkali metal hydroxide, sodium carbonate or sodium bicarbonate, at a temperature of from about 0 to 50C.

The preparation of the compounds is illustrated in the following example:

EXAMPLE 1 At 0 to 5C, a solution of 13 parts by weight of 3,5- dichlorobenzoyl chloride in 50 parts by weight of benzene is added to a solution of 11 parts by weight of lcyanoisopropylamine (95 wt. in 150 parts by weight of benzene. The mixture is stirred overnight and then washed with dilute hydrochloric acid and water. The crude N-( 1-cyanoisopropy1 )-3,S-dichlorobenzamide was obtained from the organic phase after drying with magnesium sulfate andevaporation of the solvent.

Melting point: 135to l38CjAfter crystallization from benzene the compound melts at 140 to 141C.

The compound has the following structural formula:

I 3 QC-NH-C-CEN 11 I Cl I 0 CH The following compounds were obtained in similar manner: N-(2-methoxyisopropy1)-3,5-dichlorobenzamide, m.p. 107 to 108C; N-(2-ethoxyisopropy1)-3,5-dich1orobenzamide, m.p. 77 to 79C; I N- (2-cyanoisopropy1)-3 ,S-dichlorobenzamide, m.p. 138 to 141C; N-(cyano-tert-butyl)-3,5-dichlorobenzamide,

m.p. 134 to 135C; N-(2-chloroisopropy1)-3 ,S-dichlorobenzamide, 120C;

N-[1,1,2-trimethy1butyn-(3)-y1-( 1 )-]-3,5- dichlorobenzamide,

m.p. 1l1to 112C;

3 ,S-dichlorobenzoic-[a,a-dimethy1-( B-chloroethyl amide,

m.p. 131to 132C;

3 ,5-dich1orobenzoic-[a,a-dimethy1-(B-hydroxyethyl amide,

m.p. 92 to 93C;

3 ,5-dichlorobenzoic-[ a,a,B-trimethy1propyl]-amide, m.p. 112 to 114C;

3 ,5-dich1orobenzoic-[ bicyc1o-( 2,2,1 )-hepty1]-amide, m.p. 151 to 152C;

3 ,5 -dich1orobenzoic-[amethy1-(B-ch1oroethy1)]- amide, m.p. 120C;

3 ,5-dich1orobenzoica-ch1oromethy1-( propyl) amide,

m.p. 126 to 127C; 3,5-dichlorobenzoic-[a,a-dimethy1-('y-hydroxypropy1)]amide,

m.p. to 96C;

3 ,5-dich1orobenzoic-[ a,a-diethy1-(propyny1) ]-amide, m.p. to 106C;

3 ,5'dichlorobenzoica-methyl-oz-ethyl-( propynyl amide, m.p. 94 to 95C; 3,5-dichlorobenzoic-[a-methylisobutyH-amide; 3,5-dich1orobenzoic-[a,a-dimethy1-(B- methoxyethy1)]-amide; 3,5-dichlorobenzoic-[a-ethylpropy1]-amide; 3,5-dichlorobenzoic-[a-norbornylethyll-amide;

3 ,5 -dich1orobenzoic-[ a-methylpropynyl -amide;

3 ,5-dichlorobenzoic-[ a-methy1-( B-hydroxyethyl amide;

3 ,S-dichlorobenzoic-[a-ethy1-(B-hydroxyethy1) amide; 3,5-dich1orobenzoic-[a,a-dimethy1propy1l-amide; 3,5-dich1orobenzoic-[a-ethylpropyl]-amide; 3,5-dich1orobenzoic-norbornylamide;

3 ,5 -dich1orobenzoic-[ a-ethynyl)-a-methy1benzy1]- amide;

3 ,5-dich1orobenzoic-[ a -ethynyl )-a-methy1isobuty1]- amide; 3,5-dich1orobenzoic-[a,a-dimethylbenzyl]-amide; 3,5-dich1orobenzoic-Ia,a-dimethy1isobutyll-amide;

3 ,5 -dichlorobenzoic[ a,a-dimethyl-( B-carbomethoxyethyl l-amide.

- H-CH CH CH Cl ll QC-NH-R C1 m.p. 95 t 95C m.p. 105 to 106C m.p. 95 to 96C m.p. 124 to 127C m.p. 780C m.p. 112 to 114C I 3 I-CH -CH -CH 108 to 110C to 69C 88 to 0C 124 to 126C m.p. 152 to 136C Some of the amine components which may be reacted in similar manner are given below:

5 CH-NH -S-CH2/ 2 -S-CH PIC-CH l-(n-pr'opoxy)-propylamine-2 l-(methylthio)-propylamine-2 l-(ethylthio)-propylamine-2 l-hydroxypropylamine-2 l-butyn- (2)-ylamine-2 l-hydroxybutylamine-2 l-chlorobutylamine-2 I -(E...NH

ClCH CH l-cyanopropylamine-2 nor'bornylamine 1, 1-dimethyl-2-methoxyethylamine-l 1, 1-dimethyl-2-ethoxyethylamine-1 l, l-dimethyl-2-pr'o.poxyethylamine-l l, l-dimethylethanol-2-amine-1 l, l-dimethylpr-opanol-3-amine-1 1, l-dimethylbutanol-4-amine-1 1, 1-dimethy1-2-chloroethylamine-1 l, l-bis-(hydr'oxymethyl)-ethylamine-l 1, l,1-tr'is-(hydroxymethyl)-methylamine 1, l-bis-(chloromethyl)-ethylmine(l) 1, 1, 1-tr1s-(chlor'omethyl)-mechylamine 1, l-dimethylpropen-(2)-ylamine--l 3\ CPL-NH methyl o(-aminopr-opionate O C CH O C-CNH ethyl a ohdimethylaminoacetate C H O CH The agents according to the invention may be used I [ingredient as solutions, emulsions, suspensions or dusts. The form. of application depends entirely on the purpose for goja bispida g 0 0 rasslca spp. l 10 5 35 WhlCh the agents are being used, many case t should PM annuu 100 95 95 95 ensure a fine-distribution of the active ingredient. goa trivialis 95 95 95 95 romus tcclorum 95 9O 90 90 For the preparation of solutions to be sprayed direct, Echinochloa cruygum 95 90 90 90 hydrocarbons having boiling points higher than 150C, e. g. tetrahydronaphthalene or alkylated naphthalenes, or organic liquids having boiling points higher than 150C and having one or more than one functional group, e. g. the keto group. the ether group, the ester group or the amide group, this group or these groups being attached as substituent(s) to a hydrocarbon chain or being a component of a heterocyclic ring, may be used as spray liquids.

Aqueous formulations may be prepared from emulsion concentrates, pastes or wettable powders by adding water. To prepare emulsions the ingredients as such or dissolved in a solvent may be homogenized in water or organic solvents by means of wetting or dispersing agents, e. g. polyethylene oxide adducts. Concentrates which are suitable for dilution with water may be prepared from active ingredient, emulsifying or dispersing agent and possibly solvent.

Dusts may be prepared by mixing or grinding the active ingredients with a solid carrier, e. g. kieselguhr, talc, clay or fertilizers.

The action of the new active ingredients is illustrated in the following examples.

EXAMPLE 2 An agricultural plot was sown with Soja hispida, Brassica spp., Poa annua, Poa trivialis, Bromus tectorum and Echinochloa crus-galli. The soil prepared in this manner was then immediately treated with 2 kg per hectare of each of the following active ingredients, each compound being dispersed in 500 liters of water per hectare:

l N-( l-cyanoisopropyl)-3,5-dichlorobenzamide ll N-( 2-methoxyisopropyl)-3,5-dichlorobenzamide lll N-(Z-ethoxyisopropyl)-3,5-dichlorobenzamide IV N-( 1 ,1.-dimethyl-2-butynyl)-3,5-dichlorobenzamide (comparative agent) After 4 to 5 weeks it was ascertained that active ingredients I. ll and Ill had better crop plant compatibility than IV, combined with the same good herbicidal action.

The results of the experiment are given in the following table:

0 no damage 100 complete destruction The action of the following compounds corresponds to that of I, ll and Ill: N-(2-cyanoisopropyl)-3,5-dichlorobenzamide N-(cyano-tert-butyl)-3,5-dichlorobenzamide 3,5-dichlorobenzoic-Z-chloroisopropylamide 3 ,5-dichlorobenzoic-a-hydroxy-tert-butylamide 3,5-dichlorobenzoic-a-methylisobutylamide EXAMPLE 3 An agricultural plot with Brassica spp., Poa annua, Poa trivialis and Dactylis glomerata growing on it was treated at a growth height of the plants of 2 to 8 cm with 3 kg per hectare of N-(Z-methoxyisopropyl)-3,5- dichlorobenzamide (I) and with 3 kg per hectare of N- (2-ethoxyisopropyl)-3,5-dichlorobenzamide (ll), each active ingredient being emulsified in 500 liters of water per hectare.

After 3 to 4 weeks Poa annua, Poa trivialis and Dactylis glomerata were completely withered, whereas Brassica spp. continued to grow almost undamaged.

EXAMPLE 4 90 parts by weight of compound I from Example 2 is mixed with 10 parts by weight of N-methyl-apyrrolidone. A mixture is obtained which is suitablefor application in the form of very fine drops.

EXAMPLE 5 20 parts by weight of compound ll from Example 2 is dissolved in a mixture consisting of parts by weight of xylene, 10 parts by weight of the adduct of 8 to 10 moles of ethylene oxide to 1 mole ofoleic acid-N- monoethanolamide, 5 parts by weight of the calcium salt of dodecylbenzenesulfonic acid, and 5 parts by weight of the adduct of 40 moles of ethylene oxide to 1 mole of castor oil. By pouring the solution into l00,000 parts by weight of water and uniformly distributing it therein, an aqueous dispersion is obtained containing 0.20 percent by weight of the active ingredient.

EXAMPLE 6 20 parts by weight of compound [II from Example 2 is dissolved in a mixture consisting of 40 parts by weight of cyclohexanone, 30 parts by weight of isobutanol, 20 parts by weight of the adduct of 7 moles of ethylene oxide to 1 mole of isooctylphenol, and 10 parts by weight of the adduct of 40 moles of ethylene oxide to 1 mole of castor oil. By pouring the solution into 100,000 parts by weight of water and uniformly distributing it therein, an aqueous dispersion is obtained con- .taining 0.02 percent by weight of the active ingredient.

EXAMPLE 7 20 parts by weight of compound I from Example 2 is dissolved in a mixture consisting of 25 parts by weight of cyclohexanol, 65 parts by weight of a mineral oil fraction having a boiling point between 210 and 280C, and 10 parts by weight of the adduct of 40 moles of ethylene oxide to 1 mole of castor oil. By pouring the solution into 100,000 parts by weight of water and uniformly distributing it therein, an aqueous dispersion is obtained containing 0.02 percent by weight of the active ingredient.

EXAMPLE 8 EXAMPLE 9 3 parts by weight of compound 1 from Example 2 is intimately mixed with 97 parts by weight of-particulate kaolin. A dust is obtained containing 3 percent by weight of the active ingredient.

EXAMPLE 10 30 parts by weight of compound 11 from Example 2 is intimately mixed with a mixture consisting of 92 parts by weight of powdered silica gel and 8 parts by weight of paraffin oil which has been sprayed onto the surface of this silica gel. A formulation of the active ingredient is obtained having good adherence.

We claim: 1. The compound of the formula where R is alkyl of 3 to 4 carbon atoms branched on the carbon atom in a-position to nitrogen, said alkyl being substituted by cyano.

2. N-( l-cyanoisopropyl)-3,5-dichlorobenzamide. 3. N-(2-cyanoisopropyl )-3,5-dichlorobenzamide.

4. N-(cyano-tert-butyl)-3,5-dichlorobenzamide. 

1. THE COMPOUND OF THE FORMULA
 2. N-(1-cyanoisopropyl)-3,5-dichlorobenzamide.
 3. N-(2-cyanoisopropyl)-3,5-dichlorobenzamide.
 4. N-(cyano-tert-butyl)-3,5-dichlorobenzamide. 